US6908982B2 - Amino composition and process for producing the same - Google Patents
Amino composition and process for producing the same Download PDFInfo
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- US6908982B2 US6908982B2 US10/463,594 US46359403A US6908982B2 US 6908982 B2 US6908982 B2 US 6908982B2 US 46359403 A US46359403 A US 46359403A US 6908982 B2 US6908982 B2 US 6908982B2
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- US
- United States
- Prior art keywords
- epoxy resin
- amino
- composition
- diamine
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime, expires
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- 239000000203 mixture Substances 0.000 title claims abstract description 166
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 125
- 238000000034 method Methods 0.000 title claims description 13
- 230000008569 process Effects 0.000 title claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 130
- 239000003822 epoxy resin Substances 0.000 claims abstract description 128
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 150000004985 diamines Chemical class 0.000 claims abstract description 57
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- -1 amino compound Chemical class 0.000 claims abstract description 27
- 238000007259 addition reaction Methods 0.000 claims abstract description 14
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000010276 construction Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 125000004956 cyclohexylene group Chemical group 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 abstract description 19
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 abstract description 18
- 230000009257 reactivity Effects 0.000 abstract description 12
- 230000002542 deteriorative effect Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 30
- 239000010408 film Substances 0.000 description 30
- 238000003786 synthesis reaction Methods 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 20
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000005292 vacuum distillation Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 0 [1*]N(C*CN([2*])[3*])CCc1ccccc1 Chemical compound [1*]N(C*CN([2*])[3*])CCc1ccccc1 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- ANOPCGQVRXJHHD-UHFFFAOYSA-N 3-[3-(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]propan-1-amine Chemical compound C1OC(CCCN)OCC21COC(CCCN)OC2 ANOPCGQVRXJHHD-UHFFFAOYSA-N 0.000 description 1
- 235000007575 Calluna vulgaris Nutrition 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910013698 LiNH2 Inorganic materials 0.000 description 1
- 101100166829 Mus musculus Cenpk gene Proteins 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- BDYVWDMHYNGVGE-UHFFFAOYSA-N [2-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCCC1CN BDYVWDMHYNGVGE-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- BPSKTAWBYDTMAN-UHFFFAOYSA-N tridecane-1,13-diamine Chemical compound NCCCCCCCCCCCCCN BPSKTAWBYDTMAN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/16—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings
- C07C211/18—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings containing at least two amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
- C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to an amino composition containing a certain amino compound as a main component, a process for producing the same and the use thereof.
- the amino composition when it is used as a curing agent for epoxy resin, provides a long pot life and an excellent appearance of a coating film to an epoxy resin composition without deteriorating its reactivity. Therefore, this amino composition is applicable to a curing agent for epoxy resin and a raw material thereof to be utilized in the field using epoxy resin including use as a coating material, use as a material for civil engineering and construction, use as an adhesive, use as a material for electricity and electronics, and use as a composite material. Further, this amino composition is applicable to a chain extender for polyurethane resin and a raw material thereof to be utilized in a field using polyurethane resin including use as foam, elastomer, coating adhesive, fiber, heather and water proof material.
- Room temperature curing epoxy resin composition using these curing agent for epoxy resin are particularly utilized widely in a field of coating material such as a corrosion-resistant paint for ship, bridge and land and marine iron structure, and a field of civil engineering and construction such as lining, reinforcement and repair of concrete structure, a flooring material of building, lining of water supplying facility and sewerage, pavior, and adhesive material.
- a field of coating material such as a corrosion-resistant paint for ship, bridge and land and marine iron structure
- a field of civil engineering and construction such as lining, reinforcement and repair of concrete structure, a flooring material of building, lining of water supplying facility and sewerage, pavior, and adhesive material.
- amino compounds are as follows: aliphatic polyamino compound such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine; aliphatic polyamino compound having aromatic ring such as xylylenediamine; alicyclic polyamino compound such as menthenediamine, isophoronediamine, bis(aminomethyl)cyclohexane, N-aminomethylpiperazine; aromatic polyamino compound such as phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone; other polyamino compounds such as polyamino compound having polyether framework, polyamino compound having norbornane framework. These polyamino compounds have their own characteristic features respectively caused by the reactivity of their amino groups, namely their active hydrogen. Therefore, these polyamino compounds are used as a curing agent for epoxy
- a diamine represented by the formula (1) or a curing agent for epoxy resin using the diamine as a raw material have a feature that they are suitable for curing at relatively low temperature, since their reactivity with an epoxy resin is higher and the curing speed of an epoxy resin composition is faster than other polyamino compounds or a curing agent for epoxy resin using the same as a raw material. Further, they have features to provide an excellent curing property of an epoxy resin composition, an excellent performance of cured coating film of epoxy resin, an excellent physical property of an epoxy resin cured product and an excellent adhesion property of an epoxy resin cured product and the like. Especially, when used as a coating material, they have features to provide a coating film excellent in both gloss and leveling and a cured product excellent in both water resistance and chemical resistance.
- an epoxy resin composition using a diamine represented by the formula (1) or a curing agent for epoxy resin using the diamine as a raw material has defects that it exhibits a short pot life and its workability is inferior when it is cured at room temperature. Further, it has defect that a performance of cured coating film of epoxy resin or a physical property and an adhesion property of an epoxy resin cured product occasionally deteriorates because such epoxy resin composition easily produces carbamate or carbonate by absorbing carbon dioxide or water vapor in the atmosphere. Particularly, it has defects that the appearance of a coating film tends to be inferior by the phenomena of whitening or stickiness.
- An object of the present invention is to provide an amino composition which provides, when used as a curing agent for epoxy resin, a long pot life and an excellent appearance of a coating film to an epoxy resin composition without deteriorating the reactivity of the composition, and a process for producing the same.
- Another object of the present invention is to provide a curing agent for epoxy resin which provides an excellent performance of cured coating film of epoxy resin, an excellent physical property of an epoxy resin cured product and an excellent adhesion property of an epoxy resin cured product, to provide an epoxy resin composition containing the curing agent, and to provide an epoxy resin cured coating film and an epoxy resin cured product obtained by curing the epoxy resin composition, which are suitable for a use as a coating material and a material for civil engineering and construction.
- an amino composition obtained by addition reaction of the diamine represented by the formula (1) and styrene in which a particular amino compound that is an addition product out of several kinds of addition products having different number of addition molecules and different addition structure is comprised in the certain ratio and the content of the unreacted diamine represented by the formula (1) is below a certain amount provides a long pot life and an excellent appearance of a coating film to an epoxy resin composition without deteriorating the reactivity of the composition when it is used as a curing agent for epoxy resin, and further provides an excellent performance of cured coating film of epoxy resin, an excellent physical property of an epoxy resin cured product and an excellent adhesion property of an epoxy resin cured product and is suitable for a use as an epoxy resin coating material and a material for civil engineering and construction, and have accomplished the present invention.
- the present invention provides an amino composition described in the following 1)-2), a process for producing an amino composition described in 3), a curing agent for epoxy resin described in 4), an epoxy resin composition described in 5)-7), and an epoxy resin cured product described in 8).
- the amino composition of the present invention is obtained by addition reaction of the diamine represented by the formula (1) with styrene and comprises at least one amino compound selected from the group of amino compounds represented by the formula (2) as a main component.
- the group of amino compounds represented by the formula (2) is consisted of an addition product wherein R1, R2, and R3 are all hydrogen (1-addition product), an addition product wherein any two of R1-R3 are hydrogen and one is a phenethyl group (2-addition product), an addition product wherein any two of R1-R3 are phenethyl groups and one is hydrogen (3-addition product), and an addition product wherein R1, R2, and R3 are all phenethyl groups (4-addition product).
- the amino compound(s) contained in the amino composition of the present invention is(are) selected from the above group of amino compounds.
- Example of diamine represented by the formula (1) to be used in the present invention include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, and 1,4-bis(aminomethyl)cyclohexane, among which metaxylylenediamine and 1,3-bis(aminomethyl)cyclohexane are particularly preferable. Each of them may be used individually or plural of them may be used.
- other polyamino compounds may be mixed to the diamine represented by the formula (1).
- the amount of other polyamino compounds to be mixed is larger than the amount of diamine represented by the formula (1), the features of the amino composition of the present invention using diamine represented by the formula (1) to provide an epoxy resin cured coating film excellent in both gloss and leveling and to provide a cured product excellent in both water resistance and chemical resistance cannot be maintained. Therefore, it is preferable that the amount of other polyamino compounds is 1 part by weight or below per 1 part by weight of diamine represented by the formula (1).
- Examples of other polyamino compound to be mixed with diamine represented by the formula (1) include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine and polyoxyalkylenepolyamine; alicyclic polyamines such as isophoronediamine, norbornanediamine, 1,4-diaminocyclohexane and di(aminohexyl)methane; aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone and heterocyclc polyamines such as N-aminoethylpiperazine and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.
- aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine and polyoxy
- the amino compound of the present invention is a compound or the mixture of compounds selected from the group of the amino compounds represented by the formula (2). Since the amino composition of the present invention is obtained by addition reaction of the above-mentioned diamine and styrene, it usually is a mixture which contains unreacted diamine represented by the formula (1) and the like other than the amino compound(s) selected from the group of the amino compounds represented by the formula (2).
- the content of diamine represented by the formula (1) in the amino composition is less than 15% by weight, preferably less than 5% by weight, more preferably less than 2% by weight based upon the total weight of the amino composition. The lower limits of the content of diamine is not limited.
- the content of the addition product wherein R1, R2, and R3 are all hydrogen (1-addition product) is 50 to 100% by weight, preferably 60 to 100% by weight based upon the total weight of the amino compound(s) selected from the group of the amino compounds represented by the formula (2).
- the preferable higher limit of the proportion of 1-addition product based upon the total weight of the amino compound(s) selected from the group of the amino compounds represented by the formula (2) is not limited.
- an amino composition of the present invention it is preferable to carry out addition reaction of diamine represented by the formula (1) and styrene by adjusting the reaction mole ratio of styrene and diamine (styrene/diamine) in the range of 0.25 to 1.75. Less than 0.25 of the reaction mole ratio is unfavorable because the content of unreacted diamine in the amino composition is increased and it becomes difficult to remove the unreacted diamine by extraction or it takes time to remove the unreacted diamine by distillation.
- More than 1.75 of the reaction mole ratio is unfavorable because the content of 1-addition product in which R1, R2, and R3 are all hydrogen easily becomes less than 50% by weight based upon the total weight of the amino compounds represented by the formula (2) and the reactivity of the epoxy resin composition may easily deteriorate.
- Preferable catalyst to be used in the process of producing amino composition of present invention includes any substance exhibiting strong basicity.
- examples of such catalyst include alkaline metal, alkaline metal amide and alkylated alkaline metal.
- alkaline metal amide by the general formula MNRR′ wherein M is an alkaline metal, N is nitrogen and R and R′ are, each independently, hydrogen or an alkyl group, is preferable and lithium amide (LiNH 2 ) is more preferable.
- the amount of the catalyst depends on conditions such as species of raw material, reaction proportion and reaction temperature, and is usually 0.05 to 5% by weight and preferably 0.1 to 3% by weight based upon the total weight of raw material. When the amount of catalyst is below 0.05% by weight, the reaction rate may decrease, whereas above 5% by weight, the reaction rate does not increase which is not economical.
- the reaction temperature is not limited on the condition that it is a melting point of diamine represented by the formula (1) or above. Usually, it is 25 to 150° C. and preferably 50 to 100° C. When the reaction temperature is below 25° C., the reaction rate of diamine represented by the formula (1) and styrene is slow, whereas above 150° C., since a polymer of styrene is produced as a by-product, it is desirable to select the reaction temperature depending on species of raw material, reaction proportion and species and amount of the catalyst.
- the strong base catalyst such as alkaline metal amide readily reacts with moisture or carbon dioxide in air. Therefore, it is preferable to exclude the influence of moisture and carbon dioxide by carrying out the reaction in an inert gas such as nitrogen, helium or argon.
- the reaction liquid thus obtained comprises amino compound(s) produced by the reaction and catalyst.
- the reaction liquid usually further contains unreacted diamine raw material and/or unreacted styrene.
- alkaline metal amide is used as the catalyst, it is possible to change the alkaline metal amide to a readily removable salt thereof by adding acids such as hydrochloric acid, hydrogen chloride gas and acetic acid, alcohols such as methanol and ethanol or water, and then filtrate it.
- acids such as hydrochloric acid, hydrogen chloride gas and acetic acid
- alcohols such as methanol and ethanol or water
- the amino composition obtained after the reaction is completed and the precipitate such as used catalyst is removed usually contains unreacted diamine represented by the formula (1) as mentioned above.
- the content of the unreacted diamine is 15% by weight or more, it is desirable to remove the diamine so that the content of the diamine become below 15% by weight, preferably below 5% by weight, more preferably 2% by weight.
- the removal of the diamine can be carried out by distillation or extraction. Though the method of distillation is not limited, the removal is easily carried out by distillation under reduced pressure.
- solvent is not limited as long as the diamine is soluble and the group of amino compounds represented by the formula (2) is not solved to the solvent.
- the preferable solvent is Water.
- the amino composition of the present invention has reactivity with an epoxy resin or isocyanate and is useful as a curing agent for epoxy resin and a chain extender for polyurethane resin. Particularly, when the amino composition is applied to a curing agent for epoxy resin, it provides a long pot life and an excellent appearance of a coating film to an epoxy resin composition without deteriorating the reactivity of the composition.
- the curing agent may be used alone or as a mixture with other polyamino curing agents for epoxy resin.
- the mixing ratio is not limited, it is preferable to select the ratio within limits not losing the characteristic of the amino composition of the present invention.
- the epoxy resin composition containing the amino composition of the present invention as a curing agent for epoxy resin provides an excellent appearance of coating film and an excellent physical property of cured product. Therefore, it is especially useful as a coating material or a material for civil engineering and construction.
- epoxy resin used for an epoxy resin composition useful as a coating material or a material for civil engineering and construction preferably include bisphenol A type epoxy resin and bisphenol F type epoxy resin which may be used alone or as a mixture with each other.
- usable epoxy resin is not limited and any epoxy resin having glycidyl group reactive with active hydrogen of the amino composition of the present invention containing in the curing agent for epoxy resin can be used.
- the content of the amino composition in an epoxy resin composition is not limited, it is preferable to mix 0.7 to 1.2 active hydrogen equivalent of the amino composition based upon the total epoxy equivalent of epoxy resin. Further, components for modification such as filler and plasticizer, components for adjusting fluidity such as diluent and thixotropic agent, and other ingredients such as pigment, leveling agent, and tackifier may be added to the epoxy resin composition of the present invention depending on the intended use.
- Evaluation of the property of an epoxy resin composition and a cured product thereof is carried out by the following method.
- Epoxy resin composition was coated on a glass plate (25 ⁇ 300 ⁇ 2 mm) with thickness of 76 micron under the conditions of 23° C. and 50% RH.
- the time required to reach each drying stage was measured by RCI drying meter of drying time. The shorter the time required is, the higher the curing property is.
- Epoxy resin composition was coated on a steel plate with thickness of 200 micron under the conditions of 23° C. and 50% RH. After 7 days of curing, the appearance of coating film such as whitening and stickiness was observed.
- Epoxy resin composition was coated on a steel plate with thickness of 200 micron under the conditions of 23° C. and 50% RH. Intercoat Adhesion is evaluated with the coating film prepared by coating upper layer 1 day after coating lower layer.
- the coating film after 1+7 days of curing is evaluated referring to X cut-tape method of JIS K 5400.
- Coated steel plate after 7 days of curing was dipped in each chemical (sodium hydroxide with the concentration of 10%, sulfuric acid with the concentration of 10%, acetic acid with the concentration of 10%, methanol, and toluene) for 7 days under the condition of 23° C. Change of the appearance of the coating film was evaluated visually. Salt spray test was carried out being compliant with JIS K 5400.
- An epoxy resin composition was cured for 7 days under the conditions of 23° C. and 50% RH to prepare each test peace.
- An epoxy resin composition was cured for 7 days under the conditions of 23° C. and 50% RH to prepare each test peace.
- an epoxy resin composition was cured for 7 days under the conditions of 23° C. and 85% RH to prepare each test peace.
- 1,3-BAC 1,3-bis(aminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Co., Inc., in Japan
- 1,3-BAC 1,3-bis(aminomethyl)cyclohexane
- lithium amide 2.0 g (0.09 mol)
- a flask similar as the one used in Example of Synthesis 1 was charged to a flask similar as the one used in Example of Synthesis 1, and its interior temperature was raised to 80° C. in a nitrogen gas stream with stirring. Keeping the temperature at 80° C., 364.7 g (3.5 mol) of styrene was added thereto dropwise over 1.5 hours. After the completion of dropwise addition, its interior temperature was maintained to 80° C. for one hour.
- Epoxy resin compositions were prepared by mixing bisphenol A type liquid epoxy resin with an epoxy equivalent of 190, manufactured by Japan Epoxy Resins Co., Ltd., trade name; Epicoat 828, and amino compositions A to E obtained by Examples of Synthesis 1 to 5 used as a curing agent for epoxy resin at a ratio shown in Table 1.
- Example 1 Example 2
- Example 3 Example 4
- Example 5 Epoxy resin composition (g) Epicoat 828 100 100 100 100 100 100 Amino compound A 48 Amino compound B 55 Amino compound C 42 Amino compound D 51 Amino compound E 59 Pot life (min) 280 340 191 225 290 Curing property (hr:min) set-to-touch 3:45 4:15 3:45 5:15 6:00 dust free 6:45 7:30 6:00 8:30 9:15 dry through 15:15 16:45 20:00 17:30 18:30 Appearance whitening not observed not observed not observed not observed not observed not observed stickiness not observed not observed not observed not observed not observed not observed not observed not observed not observed not observed not observed
- Example 1 Example 7
- Example 2 Example 3 Epoxy resin composition (g) Epicoat 828 100 100 100 100 100 100 Amino compound F 44 Amino compound G 75 Amino compound H 45 Amino compound I 76 Amino compound J 42 Pot life (min) 175 — 130 — — Curing property (hr:min) set-to-touch 3:00 6:15 4:15 9:00 4:15 dust free 5:45 10:00 7:15 12:15 6:45 dry through 14:00 >24:00 15:45 >24:00 >24:00 Appearance whitening observed observed not observed not observed not observed stickiness not observed not observed observed observed observed observed observed observed observed observed observed
- Unreacted MXDA was removed by vacuum distillation from 600 g of amino composition J obtained by the manner described in Example of Synthesis 10, whereby 486.4 g of Amino composition K was obtained.
- the content of unreacted MXDA in the amino composition K was 0.7% by weight base upon the total weight of the amino composition.
- the content of addition product wherein R1, R2, and R3 are all hydrogen was 55% by weight based upon the total weight of the group of amino compounds represented by the formula (2).
- Unreacted 1,3-BAC was removed by vacuum distillation from 600 g of amino composition L obtained by Example of Synthesis 12, whereby 474.8 g of Amino composition M was obtained.
- the content of unreacted 1,3-BAC in the amino composition M was 0.6% by weight.
- the content of addition product wherein R1, R2, and R3 are all hydrogen was 55% by weight based upon the total weight of the group of amino compounds represented by the formula (2).
- Epoxy resin compositions were prepared by mixing bisphenol A type liquid epoxy resin with an epoxy equivalent of 190, manufactured by Japan Epoxy Resins Co., Ltd., trade name; Epicoat 828, and amino compositions K and M obtained by Examples of Synthesis 11 and 13 used as a curing agent for epoxy resin at a ratio shown in Table 3.
- the epoxy resin compositions thus obtained were cured under the conditions of the temperature of 23° C. and 50% RH to prepare cured coating film and cured product with which evaluation of property was carried out.
- Example 9 Epoxy resin composition (g) Epicoat 828 100 100 Amino composition K 55 Amino composition M 56 Property of cured coating film Appearance Gloss ⁇ ⁇ Clarity ⁇ ⁇ Leveling ⁇ ⁇ Drying characteristics ⁇ ⁇ Intercoat adhesion ⁇ ⁇ Water resistance ⁇ / ⁇ / ⁇ ⁇ / ⁇ (1/4/7 days) Chemical resistance 10% sodium hydroxide ⁇ ⁇ 10% sulfuric acid ⁇ ⁇ 10% acetic acid ⁇ ⁇ methanol ⁇ ⁇ toluene ⁇ ⁇ solt spray test ⁇ ⁇ Physical property of cured product Tensile strength (Mpa) 36.8 35.3 Tensile modulus (Gpa) 2.31 2.22 Flexural strength (Mpa) 69.4 70.1 Flexural modulus (Gpa) 2.05 2.31 Compressive strength (Mpa) 78.6 79.7 Compressive modulus (Gpa) 2.54 2.56 Adhesion property of cured product Tensile shear adhesion strength (Mpa) 36.
- amino composition obtained by addition reaction of diamine represented by the formula (1) with styrene wherein the content of unreacted diamine represented by the formula (1) is less than a certain amount and the content of addition product represented by the formula (2) in which R1, R2 and R3 are all hydrogen is in the range of certain amount
- amino composition obtained by addition reaction of diamine represented by the formula (1) with styrene in a certain range of reaction ratio provides a long pot life and an excellent appearance of a coating film to an epoxy resin composition without deteriorating the reactivity of the composition when it is used as a curing agent for epoxy resin.
- an epoxy resin composition using a curing agent for epoxy resin comprising an amino composition of the present invention provides an excellent performance of cured coating film of epoxy resin, an excellent physical property of an epoxy resin cured product and an excellent adhesion property of an epoxy resin cured product, and is suitable for use as epoxy resin coating material and use in the field of civil engineering and construction.
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JP2002176977 | 2002-06-18 | ||
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JP2002176980 | 2002-06-18 |
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US (1) | US6908982B2 (fr) |
EP (1) | EP1375554B1 (fr) |
CN (1) | CN1267468C (fr) |
DE (1) | DE60316383T2 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040171770A1 (en) * | 2003-02-13 | 2004-09-02 | Hisayuki Kuwahara | Low-temperature curable epoxy resin curing agent and epoxy resin composition |
US20080275191A1 (en) * | 2007-04-26 | 2008-11-06 | Air Products And Chemicals, Inc. | New Amine Composition |
US8063157B2 (en) | 2004-06-21 | 2011-11-22 | Huntsman Advanced Materials Americas Llc | Curing agents for epoxy resins |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US20120142816A1 (en) * | 2006-11-20 | 2012-06-07 | Dow Global Technologies Inc | Novel epoxy hardeners with improved cure and polymers with enhanced coating properties |
US8512594B2 (en) * | 2008-08-25 | 2013-08-20 | Air Products And Chemicals, Inc. | Curing agent of N,N′-dimethyl-meta-xylylenediamine and multifunctional amin(s) |
CN104159946A (zh) * | 2012-03-09 | 2014-11-19 | 建筑研究和技术有限公司 | 可胺固化的环氧树脂组合物 |
WO2013131776A1 (fr) * | 2012-03-09 | 2013-09-12 | Construction Research & Technology Gmbh | Composition de résine époxyde durcissable par des amines |
JP6886641B2 (ja) * | 2015-03-31 | 2021-06-16 | 三菱瓦斯化学株式会社 | エポキシ樹脂硬化剤、エポキシ樹脂組成物、塗料、土木建築用部材、硬化物及び複合材料、並びにエポキシ樹脂硬化剤の製造方法 |
TW202003445A (zh) * | 2018-05-31 | 2020-01-16 | 日商三菱瓦斯化學股份有限公司 | 化合物之製造方法、化合物、環氧硬化劑及胺組成物之製造方法 |
CN109852314B (zh) * | 2019-03-11 | 2021-01-05 | 上海域金澜优实业有限公司 | 一种耐白化美缝剂 |
CN113956165A (zh) * | 2021-10-28 | 2022-01-21 | 长沙友兴盟进出口贸易有限公司 | 一种间苯二甲胺改性工艺 |
CN114163334B (zh) * | 2021-11-18 | 2023-07-14 | 万华化学集团股份有限公司 | 一种改性脂环胺固化剂及其制备方法 |
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- 2003-06-17 DE DE60316383T patent/DE60316383T2/de not_active Expired - Lifetime
- 2003-06-17 EP EP03013367A patent/EP1375554B1/fr not_active Expired - Lifetime
- 2003-06-18 US US10/463,594 patent/US6908982B2/en not_active Expired - Lifetime
- 2003-06-18 CN CNB031494285A patent/CN1267468C/zh not_active Expired - Lifetime
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JPH1045878A (ja) | 1996-08-07 | 1998-02-17 | Fuji Kasei Kogyo Kk | 硬化性エポキシ樹脂組成物 |
US20020055605A1 (en) | 2000-09-12 | 2002-05-09 | Mitsubishi Gas Chemical Company, Inc. | Amino compound and process for producing the same |
US6562934B2 (en) * | 2000-09-12 | 2003-05-13 | Mitsubishi Gas Chemical Company, Inc. | Amino compound and process for producing the same |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040171770A1 (en) * | 2003-02-13 | 2004-09-02 | Hisayuki Kuwahara | Low-temperature curable epoxy resin curing agent and epoxy resin composition |
US20070155915A1 (en) * | 2003-02-13 | 2007-07-05 | Hisayuki Kuwahara | Low-temperature curable epoxy resin curing agent and epoxy resin composition |
US7396902B2 (en) * | 2003-02-13 | 2008-07-08 | Mitsubishi Gas Chemical Company, Inc. | Epoxy resin curing agent of aliphatic diamine/styrene addition product |
US7414097B2 (en) | 2003-02-13 | 2008-08-19 | Mitsubishi Gas Chemical Company, Inc. | Curing epoxy resin with aliphatic diamine-styrene product and carboxyl- and hydroxyl-containing accelerator |
US8063157B2 (en) | 2004-06-21 | 2011-11-22 | Huntsman Advanced Materials Americas Llc | Curing agents for epoxy resins |
US20080275191A1 (en) * | 2007-04-26 | 2008-11-06 | Air Products And Chemicals, Inc. | New Amine Composition |
US9133306B2 (en) * | 2007-04-26 | 2015-09-15 | Air Products And Chemicals, Inc. | Amine composition |
US9944836B2 (en) | 2007-04-26 | 2018-04-17 | Evonik Degussa Gmbh | Amine composition |
Also Published As
Publication number | Publication date |
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EP1375554B1 (fr) | 2007-09-19 |
DE60316383D1 (de) | 2007-10-31 |
US20040044176A1 (en) | 2004-03-04 |
DE60316383T2 (de) | 2008-06-12 |
EP1375554A1 (fr) | 2004-01-02 |
CN1468883A (zh) | 2004-01-21 |
CN1267468C (zh) | 2006-08-02 |
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